In one aspect, this invention relates to the separation of saturated cycloaliphatic hydrocarbons (cycloalkanes, naphthenes) from close-boiling paraffinic hydrocarbons (alkanes, paraffins) by extractive distillation. In another aspect, this invention relates to the separation of cycloalkanes from alkanes by liquid-liquid extraction. In still another aspect, this invention relates to the separation of aromatic hydrocarbons from close-boiling alkanes by extractive distillation. In a further aspect, this invention relates to the separation of aromatic hydrocarbons from alkanes by liquid-liquid extraction.
Extractive distillation is a well known technique for separating mixtures of components having a relative volatility close to unity (i.e., having nearly equal volatility and having nearly the same boiling point). It is difficult to separate the components of such mixtures by conventional fractional distillation. In extractive distillation, a solvent is introduced into a distillation column above the entry point of the feed mixture which is to be separated. The solvent affects the volatility of the higher boiling feed component(s) sufficiently to facilitate the separation of the various feed components by distillation and exits with the bottoms fraction, as has been described in the article entitled "Extractive Distillation Saves Energy" by Ian Sucksmith, Chemical Engineering, June 28, 1982, pages 91-95, the disclosure of which is herein incorporated by reference. Other literature sources on extractive distillation techniques include the "Handbook of Separation Technques for Chemical Engineers" by Philip A. Schweitzer, McGraw-Hill Book Company, 1979, pages 1-135 to 1-143; and Perry's Chemical Engineers Handbook, 6th Edition, McGraw-Hill Book Company 1984, pages 13-53 to 13-57, the disclosures of which are herein incorporated by reference.
The separation of naphthenes (cycloparaffins), in particular cyclohexane, from close-boiling paraffins (alkanes) by extractive distillation is known and has been described in the patent literature, such as in U.S. Pat. Nos. 2,508,723; 2,771,494; 2,846,485; 2,891,894; 3,034,969 and 4,053,369, the entire disclosures of which are herein incorporated by reference. The separation of aromatics from close-boiling alkanes by extractive distillation is described in U.S. Pat. Nos. 3,591,490 and 4,278,505, the entire disclosures of which are herein incorporated by reference. However, there is an ever present need to develop more selective solvents than those presently known in the extractive distillation of mixtures of close-boiling paraffins and naphthenes and/or aromatics. In particular, it is highly desirable to develop improved extractive distillation processes for producing cyclohexane of high purity, which is a starting material for making nylon and other useful polymeric materials.
The separation of aromatic and non-aromatic hydrocarbons by liquid-liquid extraction is also well known, and has been described in the patent literature, e.g. in U.S. Pat. Nos. 2,949,422 and 3,193,489, the entire disclosures of which are herein incorporated by reference. However, there is a present need to use more effective solvents for such liquid-liquid extraction processes.